Polyaniline is one of the oldest polymers known, and has been prepared in the form of emeraldine hydrochloride by oxidizing an aqueous hydrochloric acid solution of aniline with ammonium peroxy disulfate at ambient temperature. Polyaniline is a cheap, highly electrically conducted polymer, but is processable with difficulty in its powder form. Conventionally, making such conjugated conducting polymers oil-soluble and processible has been a very difficult problem.
S. Li et al., Synth. Met. 20(2), 141-9 (1987) discloses the graft polymerization of polyaniline with polyaminostyrene to form polyaniline soluble in common organic solvents (DMF and DMSO, and slightly soluble in methanol and trichloromethane). This procedure involved the nitration of polystyrene (of 120,000 molecular weight) with either fuming nitric acid or a chloroform solution of 100% nitric acid and acetic anhydride. The resulting polynitrostyrene was hydrogenated with phenylhydrazine under nitrogen to form the polyaminostyrene.
S. Li, "Synthesis and Characterization of Soluble Polyaniline," Syn. Met. 29 (E329-E336) (1989) reports three general synthetic routes for the solubilization of polyaniline in DMF and DMSO. The experimental synthesis employed either formation of block polyaniline (employing either para-aminobenzenesulfonylchloride/poly(ethylene glycol) reaction products or para-aminobenzoyl chloride/poly(ethylene glycol) reaction products, and the preparation of graft polyanilines by polymerization of aniline on polyaminostyrene, polyacrylamides or polyepichlorohydrin.
S. P. Armes et al., "The Synthesis of Polymeric Surfactants for the Preparation of Sterically-Stabilized Polyaniline Colloids," Polym. Mater. Sci. Eng., 60, 751-753 (1989) discloses copolymerization of 2- or 4-vinyl pyridine with para-aminostyrene.
T. Kobayashi et al., "Polyaniline Film-Coated Electrodes as Electrochromic Display Devices," J. Electroanal. Chem. 161, 419-423 (1984) discloses evaluations of the electrochromic properties of polyaniline films.
A. G. MacDiarmid et al., "`Polyaniline`: Interconversion of Metallic and Insulating Forms," Mol. Cryst. Liq. Cryst., 121, 173-180 (1985) describes the synthesis of polyaniline powder and the conversion of this material to various insulating and metallic forms by acid/base and oxidation/reduction mechanisms.
Y. Cao et al., "Spectroscopic and Electrical Characterization of Some Aniline Oligomers and Polyaniline," Syn. Met. 16, 305-315 (1986) describes the preparation of aniline oligomers and polyaniline, and proton-doped derivatives.
W. Huang et al., "Polyaniline, a Novel Conducting Polymer," J. Chem. Soc., Faraday Trans. 1, 82, 2385-2400 (1986) discloses the chemical synthesis of polyaniline and electrochemical synthesis of polyaniline from aniline.
F. L. Lu et al., "Phenyl-Capped Octaaniline (COA): An Excellent Model for Polyaniline," JACS 108, 8311-8313 (1986) discloses the preparation of a mono-dispersed polyaniline of molecular weight of 806 and its conversion to a partially oxidized form.
F. Wudl et al., "Poly (p-phenyleneamine) Synthesis and Comparison to Polyaniline," JACS 109, 3677-3684 (1987) discloses the preparation of small polyaniline oligomers by a double condensation of para-phenyl amino-substituted anilines with diethyl succinoyl succinate and the preparation of poly(p-phenaline amine) by the reaction of succino succinic acid (2,5-dioxo-1,4-cyclohexane dicarboxylic acid) and p-phenyline diamine.
A. G. MacDiarmid et al., "The Polyanilines: Processing, Molecular Weight, Oxidation State and Derivatives," Polymer Pre-prints 30, 147-48 (1989); M. Angelopoulos et al. "Polyaniline: Solutions, Films and Oxidation State," Mol. Cryst. Liq. Cryst. 160, 151-163 (1988); A. Andreatta et al., "Electrically-Conducted Fibers of Polyaniline Spun From Solutions in Concentrated Sulfuric Acid," Syn. Met. 26, 383-389 (1988); A. Ray et al., "Polyaniline: Doping, Structure and Derivatives," Synth. Met. 29, 141-150 (1989); S. P. Armes et al., "Novel Colloidal Dispersions of Polyaniline," J. Chem. Soc., Chem. Commun. 88-89 (1989) also relate to preparation of polyaniline.
Y. Wei et al., "Synthesis and Electrochemistry of Alkyl Ring-Substituted Polyanilines," J. Phys. Chem. 93, 495-499 (1989) discloses the synthesis of poly(o-toluidine), poly(m-toluidine) and poly(o-ethylaniline), by chemical and electrochemical syntheses.
S. K. Manohar et al., "N-Substituted Derivatives of Polyaniline," Syn. Met. 29, 349-56 (1989) discloses the preparation of N-methylated polyaniline.
U.S. Pat. No. 4,604,427 relates to forming electrically conducting polymer blends by impregnating a pre-formed host polymer with a cyclic monomer such as aniline and then exposing the mixture with a chemical oxidant to form the conductive polymer reaction product within the surface layer of the host polymer.
Canadian Patent 806,736 relates to an antioxidant for hydrocarbon-type rubber which is in the form of an aromatic polymer having repeating units which consist of an NH-group attached to a difunctional aromatic group prepared by reacting either hydroquinone or para-benzoquinone with various aromatic diamines, such as para-phenylene diamine and 2,7-diamino naphthylene (page 4). The antioxidant activity of exemplary polymers were demonstrated in ethylene-propylene copolymer rubber vulcanisate (pages 7-8).
European Patent Publication 314,311 relates to the preparation of conducting articles by (a) forming a gel of a carrier polymer in a compatible solvent, b) poly-merizing, within the gel, a selected monomer, and (c) doping the article so provided. Disclosed carrier polymers include high molecular weight (M.W.&gt;100,000) flexible chain polymers, such as polyethylene, isostatic polypropylene, poly(ethylene oxide) and polystyrene, and lower molecular weight polymers (10,000-100,000) having "rigid-rod" molecules, such as aramid polymers, aromatic polyesters, PBT and PBI. The polymerization step (b) can include oxidative-coupling polymerization employing aniline. The polymeriztion step results in the formation, within the carrier polymer, of a normally intractable polymeric material derived from the selected monomer.
European Patent Publication 314,845 discloses graft copolymers characterized by oil-soluble substantially linear, carbon-carbon backbone polymer having graft polymerized thereon units derived from RNH.sub.2 monomer, wherein R is a hydrocarbon containing a polymerizable ethylenically unsaturated double bond. Illustrated amine monomers include p-aminostyrene and p-(aminomethyl) styrene.
U.S. Pat. No. 3,219,666 discloses lubricating oil dispersants comprising oil-soluble, acylated nitrogen compositions, having within its structure (A) a substantially hydrocarbon-substituted polar group wherein the substantially hydrocarbon substituent contains at least about 50 carbon atoms, and (B) a nitrogen-containing group characterized by a nitrogen atom attached directly to the polar group and which are prepared, e.g., by reacting a polyalkenyl-substituted succinic anhydride with an amine. Aniline and N-cyclohexyl-aniline are disclosed as amine reactants.